KR20220045042A - Siloxane derivatives of amino acids with surface-active properties - Google Patents

Abstract

The present disclosure provides siloxane derivatives of amino acids with surface-active properties. The amino acid may be naturally occurring or synthesized, or may be obtained through a ring-opening reaction of a lactam such as caprolactam. Amino acids can be functionalized with siloxane groups to form compounds that are surface-active and have surfactant properties. The compound has a low critical micelle concentration (CMC) as well as the ability to lower the surface tension of liquids.

Description

Siloxane derivatives of amino acids with surface-active properties

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is filed on August 22, 2019 in United States Provisional Patent Application Serial No. 62/890,341 entitled SILOXANE DERIVATIVES OF AMINO ACIDS HAVING SURFACE-ACTIVE PROPERTIES, the disclosure of which is incorporated herein by reference in its entirety. claims priority under U.S. Patent Section 35 §119(e).

Field

The present disclosure relates to siloxane derivatives of amino acids and methods for their synthesis, wherein the siloxane derivatives have surface-active properties.

Surfactants (molecules with surface-active properties) are an important class of molecules with very sought-after properties. Surfactants may be uncharged, zwitterionic, cationic or anionic. Often, these compounds are amphipathic molecules having a water-insoluble hydrophobic “tail” group and a water-soluble hydrophilic “head” group. These compounds may be adsorbed on interfaces such as an interface between two liquids, an interface between a liquid and a gas, or an interface between a liquid and a solid. For the interface between water and oil, the hydrophilic head groups extend into the water, while the hydrophobic tails extend into the oil. When added to water, the hydrophilic head group extends into the water, while the hydrophobic tail expands into the air. The presence of surfactants disrupts intermolecular interactions between water molecules and replaces them with weaker interactions between water molecules and surfactants. This lowers the surface tension and can also serve to stabilize the interface.

At sufficiently high concentrations, surfactants can form aggregates to limit exposure of the hydrophobic tail to polar solvents. One such aggregate is micelles in which molecules are arranged into spheres and interact with a polar solvent such that the hydrophobic tails are located inside the sphere and the hydrophilic heads are located outside. The effect of a given compound on surface tension and the concentration at which it forms micelles can serve to characterize the surfactant.

Surfactants are widely used in commercial applications of a wide range of formulations, from detergents to hair care products to cosmetics. Compounds with surface-active properties are used in particular as soaps, detergents, lubricants, wetting agents, foaming agents and spreading agents. Accordingly, there continues to be a need to identify and synthesize such compounds.

However, from its structure alone, it can be difficult to predict whether a given compound will have surface-active properties, such as interfacial adsorption kinetics, the minimum achievable surface tension, and/or the ability to wet hydrophobic and/or oleophobic surfaces, etc. It is also difficult to predict for other important characteristics, which are also essential to whether or not the compound will become a useful surfactant. For example, while certain amino acids and their derivatives are preferred as building blocks for surfactants, it is not intuitive to select the amino acids to use. Likewise, while some siloxanes are known to have surface-active properties, it is also very difficult to predict which siloxane will be effective. The synthesis of these compounds adds another layer of difficulty due to solubility differences due to different elements and moieties present in the same molecule. There remains a need for high-potency surfactants that can be readily synthesized on a commercial scale via a simple route.

The present disclosure provides siloxane derivatives of amino acids with surface-active properties. The amino acid may be a naturally occurring or synthetic amino acid, or may be obtained via a ring opening reaction of a molecule such as a lactam, for example caprolactam. Amino acids can be functionalized with different types of siloxane groups to form compounds with surface-active properties. Characteristically, such compounds may have a low critical micelle concentration (CMC) and/or the ability to reduce the surface tension of liquids.

The present disclosure provides a compound of Formula (I):

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

n is an integer from 1 to 12;

the terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl and C ₁ -C ₆ alkyl;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

Additional compounds provided by the present disclosure are compounds of Formula Ia:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

m is an integer from 1 to 6; The terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain is selected from the group consisting of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

Additional compounds provided by the present disclosure are compounds of Formula Ib:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

p is 5;

The terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain consists of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from the group;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

Another compound provided by the present disclosure is a compound of Formula I, wherein R ¹ and R ² are methyl.

Another compound provided by the present disclosure is a compound of Formula I, wherein n is 5.

Another compound provided by the present disclosure is a compound of Formula Ib wherein R ¹ and R ² are methyl.

Another compound provided by the present disclosure is a compound of Formula Ib wherein R ³ is hydrogen.

Another compound provided by this disclosure is a compound of Formula Ib, wherein the counterion is selected from the group consisting of chloride, bromide and iodide.

A further compound provided by the present disclosure is a compound of Formula Ib wherein the counterion is chloride.

Another compound provided by the present disclosure is a compound of Formula Ib wherein R ³ is methyl.

Another compound provided by the present disclosure is a compound of Formula Ib wherein the counterion is iodide.

Another compound provided by the present disclosure is a compound of Formula Ib wherein R ³ is oxygen.

A further compound provided by the present disclosure is a compound of Formula Ib wherein R ³ is C ₁ -C ₆ alkyl substituted with sulfonate.

One specific compound provided by this disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl) having the formula )oxy)trisiloxan-3-yl)propyl)hexanamide:

.

.

A second specific compound provided by the present disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethyl silyl)oxy)trisiloxan-3-yl)propyl)hexaminium chloride:

.

.

A third specific compound provided by the present disclosure is 3 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)tri having the formula siloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide:

.

.

A fourth specific compound provided by the present disclosure is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane having the formula -3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-amine oxide:

.

.

A fifth specific compound provided by the present disclosure is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl) oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate:

.

.

A sixth specific compound provided by the present disclosure is 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl) oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate:

.

.

The above-mentioned and other features of the present disclosure, and the manner of achieving them, will become more apparent and better understood upon reference to the following description of the embodiments in conjunction with the accompanying drawings.

1 shows a plot of surface tension versus concentration for surfactant 2 with a chloride counterion measured at pH = 7, as described in Example 1b.
2 shows a plot of surface tension versus concentration for surfactant 3 as described in Example 2b.
3 shows a plot of dynamic surface tension as a change in surface tension versus time for surfactant 3 as described in Example 2b.
4 shows a plot of surface tension versus concentration for Surfactant 4 as described in Example 3b.
5 shows a plot of dynamic surface tension as change in surface tension versus time for surfactant 4 as described in Example 3b.
6 shows a plot of surface tension versus concentration for surfactant 5 as described in Example 4b.
7 shows a plot of dynamic surface tension as a change in surface tension versus time for surfactant 5 as described in Example 4b.

As used herein, the phrase “within any range defined between any two of the above values” literally means that the value is recited before that phrase, regardless of whether the value is in the lower portion of the list or the upper portion of the list. It means that any range from any two of the values can be selected. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.

The word “alkyl,” as used herein, means any saturated carbon chain, which may be straight or branched.

As used herein, the phrase “surface-active” means that an associated compound can lower the surface tension of the medium in which it is dissolved, and/or the interfacial tension with other phases, and thus can be adsorbed to liquid/vapor and/or other interfaces. means there is The term "surfactant" can be applied to such compounds.

With respect to the term of imprecision, the terms “about” and “approximately” may be used interchangeably to refer to a measurement including any measurement that includes the stated measurement and is reasonably close to the stated measurement. A measurement reasonably close to the recited measure deviates from the recited measure by a reasonably small amount, as understood and readily ascertained by one of ordinary skill in the art. Such deviations may be due to, for example, measurement errors or minor adjustments made to optimize performance. When it is determined that one of ordinary skill in the art cannot readily ascertain a value for such a reasonably small difference, the terms "about" and "approximately" shall be understood to mean ±10% of the stated value. can

The present disclosure provides siloxane derivatives of amino acids. The amino acid may be naturally occurring or synthesized, or may be obtained from a ring-opening reaction of a lactam such as caprolactam. The compounds of the present disclosure have been shown to have surface-active properties and can be used, for example, as surfactants and wetting agents. In particular, the present disclosure provides for compounds of formula (I) set forth below:

wherein R ¹ and R ² can be the same or different and are at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl is one or more of oxygen, nitrogen or sulfur atoms; or a substituent comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

n is an integer from 1 to 12;

the terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl and C ₁ -C ₆ alkyl;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

The present disclosure further provides a compound of Formula Ia:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

m is an integer from 1 to 6;

The terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain is selected from the group consisting of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

The present disclosure further provides a compound of Formula Ib:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

p is 5;

The terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain consists of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from the group;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

One specific compound provided by this disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl) having the formula )oxy)trisiloxan-3-yl)propyl)hexanamide (surfactant 1):

.

.

A second specific compound provided by the present disclosure is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethyl silyl)oxy)trisiloxan-3-yl)propyl)hexaminium chloride (surfactant 2):

.

.

A third specific compound provided by the present disclosure is 3 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)tri having the formula siloxan-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide (surfactant 3):

.

.

A fourth specific compound provided by the present disclosure is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane having the formula -3-yl)propyl)amino)-N,N-dimethyl-6-oxohexan-1-amine oxide (surfactant 4):

.

.

In the above structure, the designation "N→O" is intended to convey a non-ionic bonding interaction between nitrogen and oxygen.

A fifth specific compound provided by the present disclosure is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl) oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (surfactant 5):

.

.

A sixth specific compound provided by the present disclosure is 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl) oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate:

.

.

These compounds can be synthesized by a variety of methods. One such method involves reacting an amino acid, such as an N-alkylated or N-acylated amino acid, with a siloxane to convert the amino acid C-terminus to the desired siloxane derivative. The amino acid N-terminus may be further protonated, alkylated or oxidized to give, for example, a quaternary amine or N-oxide.

The amino acid may be naturally occurring or synthetic, or may be derived from a ring-opening reaction of a lactam such as caprolactam. The ring-opening reaction may be an acid- or alkali-catalyzed reaction, and an example of the acid-catalyzed reaction is shown in Scheme 1 below.

Scheme 1

Amino acids may have as few as 1 or as many as 12 carbons between the N-terminus and the C-terminus. The alkyl chain may be branched or straight chain. The alkyl chain may be interrupted by nitrogen, oxygen or sulfur. The alkyl chain may be further substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen may be acylated or alkylated with one or more alkyl groups. For example, the amino acid may be 6-(dimethylamino)hexanoic acid.

The siloxane may be substituted with one or more alkoxy groups, such as methoxy, ethoxy, isopropoxy, tert-butoxy, and the like. The siloxane may be further substituted with one or more alkyl groups, such as propyl, wherein the alkyl group may be further substituted with an appropriate functional group that permits coupling of the siloxane to an amino acid, such as nitrogen. For example, the siloxane may be 3-aminopropyltris(trimethylsiloxy)silane.

Siloxane derivatives of amino acids can be synthesized as shown in Scheme 2 below. As shown, treatment of 6-aminohexanoic acid with formaldehyde in formic acid under reflux gives 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then coupled to 3-aminopropyl(trismethylsiloxy)silane in refluxing toluene to afford the desired siloxane derivative.

Scheme 2

The N-terminal nitrogen may be further derivatized to modify or improve water solubility and surface-active properties. A sample synthesis scheme, which treats the N-terminal nitrogen with hydrochloric acid to give the corresponding hydrochloride salt, is shown in Scheme 3 below.

Scheme 3

The N-terminal nitrogen may be alkylated. A sample synthesis scheme is presented below that provides the corresponding quaternary amine salt by treatment of the N-terminal nitrogen with methyl iodide.

Scheme 4

As shown in the sample synthesis scheme below, Scheme 5, the N-terminal nitrogen can be treated with hydrogen peroxide in water under reflux to give the corresponding N-oxide.

Scheme 5

The compounds of the present disclosure demonstrate surface-active properties. These properties can be measured and described by a variety of methods. One way that surfactants can be explained is the critical micelle concentration (CMC) of the molecule. CMC can be defined as the concentration of surfactant at which micelles are formed and above which all additional surfactant is incorporated into the micelles.

As the surfactant concentration increases, the surface tension decreases. When the surface is completely covered with surfactant molecules, micelles begin to form. This point represents the CMC as well as the minimum surface tension. Further addition of surfactant no longer affects the surface tension. Thus, CMC can be measured by observing the change in surface tension as a function of surfactant concentration. One method for determining this value is the Wilhemy plate method. The Wilhelmy plate is a thin iridium-platinum plate typically attached to the scale by wire, and is placed perpendicular to the air-liquid interface. The force exerted on the plate by wetting is measured using a balance. This value is then used to calculate the surface tension (γ) according to Equation 1:

Equation 1: γ = F/l cosθ

where l is the wetting perimeter (2w + 2d, where w and d are plate thickness and width, respectively) and cosθ, the contact angle between liquid and plate, is assumed to be zero in the absence of existing literature values.

Another parameter used to evaluate the performance of surfactants is dynamic surface tension. Dynamic surface tension is the value of surface tension for a specific surface or interface age. For liquids to which surfactants are added, this may be different from the equilibrium value. Immediately after the surface is created, the surface tension is equal to the surface tension of a pure liquid. As described above, surfactants reduce surface tension; Thus, the surface tension falls until an equilibrium value is reached. The time required to reach equilibrium depends on the rate of diffusion and adsorption of the surfactant.

One method of measuring dynamic surface tension relies on a bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble formed in a liquid through a capillary tube. The measured value corresponds to the surface tension at a certain surface age, the time from the onset of bubble formation to the development of maximum pressure. The dependence of surface tension on surface age can be measured by varying the rate at which bubbles are generated.

A surface-active compound can also be assessed by its ability to wet a solid substrate, measured by its contact angle. When a liquid droplet comes into contact with a solid surface in a third medium such as air, a three-phase line is formed between the liquid, gas and solid. The angle between the surface tension unit vector acting on a three-phase line and tangential to the liquid droplet and the surface is described as the contact angle. The contact angle (also known as the wetting angle) is a measure of the wettability of a solid by a liquid. In case of complete wetting, the liquid completely spreads over the solid phase and the contact angle is 0°. Wetting properties are typically measured at concentrations of 1-10x CMC for a given compound, but this is not a concentration-dependent property, so measurements of wetting properties can be measured at higher or lower concentrations.

In one method, an optical contact angle goniometer may be used to measure the contact angle. The device uses a digital camera and software to extract the contact angle by analyzing the contour shape of the liquid droplet adhering to the surface.

Potential applications for the surface-active compounds of the present disclosure include shampoos, hair conditioners, detergents, stain-free cleaning solutions, floor and carpet cleaners, graffiti removal cleaners, crop protection wetting agents, crop protection adjuvants, and wetting agents for aerosol spray coatings. formulations for use as

One of ordinary skill in the art will appreciate that small differences between the compounds can lead to substantially different surfactant properties, so that different compounds can be used with different substrates in different applications.

The following non-limiting examples are provided to demonstrate the different properties of different surfactants. In Table 1 below, abbreviations for surfactants relate to their corresponding chemical structures.

Table 1

Each of the five compounds is particularly effective as a surface-active agent useful in wetting or foaming agents, dispersing agents, emulsifying agents and detergents, among other applications.

Surfactants 1 and 2 are candidates for use as foaming agents or wetting agents in various surface cleaning and personal care product formulations.

Surfactant 3 is cationic. Such surfactants are useful both in the applications described above and in some additional special applications, such as surface treatment agents such as personal hair care products, and may also be used to create a water repellent surface.

Surfactant 4 is non-ionic and can be used in shampoos, detergents, hard surface cleaners and a variety of other surface cleaning formulations.

Surfactant 5 is zwitterionic. These surfactants are useful as co-surfactants in all of the applications described above.

The amount of a compound disclosed herein used in the formulation can be as low as about 0.001%, about 0.05%, about 0.1%, about 0.5%, about 1%, about 2%, or about 5% by weight, or as high as about 0.001% by weight. about 8%, about 10%, about 15%, about 20%, or about 25% by weight, or any range defined between any two of the above values.

Example

Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. Critical micelle concentration (CMC) was determined by the Wilhelmy plate method at 23° C. using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate. The dynamic surface tension was determined using a bubble pressure tensiometer (Kruess BP100, Kruess GmbH) at 23°C. The contact angle was determined using an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

Example 1a:

6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide (interfacial Active agents 1) and 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N -Synthesis of dimethyl-6-oxohexane-1-aminium salt (surfactant 2)

6-(dimethylamino)hexanoic acid (2.00 g, 12.56 mmol, 1 equiv) was dissolved in toluene (50 mL) in a 100 mL round bottom boiling flask equipped with a Dean Stark trap, followed by 3-aminopropyl Tris(trimethylsiloxy)silane (5.48 mL, 13.81 mmol, 1.1 equiv) was added. The reaction vessel was heated and the reaction refluxed for 24 hours until no more water was separated from the Dean Stark tube. The solvent was removed in vacuo to give Surfactant 1 as a yellow oil in 94% yield.

¹ H NMR (500 MHz, DMSO) δ: 0.09 (s, 27H), 0.28-0.31 (m, 2H), 1.12-1.26 (m, 2H), 1.27-1.30 (m, 4H), 1.38-1.41 (m) , 2H), 1.94 (t, J = 7.3 Hz, 2H), 2.00 (s, 6H), 2.06 - 2.03 (m, 2H), 2.89 (dd, J = 12.9, 6.8 Hz, 2H).

In the neutral form, surfactant 1 is slightly soluble in pure water without the addition of hydrotropes or other surfactants, but it becomes surfactant after protonation in weakly acidic conditions (surfactant 2). Acidic conditions can be created by adding any acid or acidic buffer in the pH 4-7 range. Surfactant 2 can also be prepared by sparging gaseous HCl in toluene in a non-aqueous solution, for example in the presence of surfactant 1.

Example 1b:

Determination of Critical Micellar Concentration (CMC) of Surfactant 2

The critical micelle concentration (CMC) for Surfactant 2 with chloride counterion was tested and was determined to be about 2 mmol. The plateau value of the minimum surface tension achievable by this surfactant is about 23 mN/m. 1 is a plot of these results, showing surface tension versus concentration.

Example 2a:

6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N,N-trimethyl Synthesis of -6-oxohexane-1-aminium iodide (surfactant 3)

Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv) was dissolved in acetonitrile (10 mL) in a 100 mL round bottom flask. Next, Na ₂ CO ₃ (0.26 g, 2.42 mmol, 1.2 equiv) was added and the mixture was stirred for 10 min. Methyl iodide (0.377 mL, 6.06 mmol, 3 equiv) was added and the reaction heated at 40° C. for 24 h. The cooled reaction mixture was filtered and the solvent was removed in vacuo to give Surfactant 3 as a pale yellow solid in quantitative yield.

-H NMR ⁽ 500 MHz, DMSO) δ 0.09 (s, 27H), 0.38-0.42 (m, 2H), 1.23-1.26 (m, 2H), 1.37-1.40 (m, 2H), 1.52-1.55 (m, 2H), 1.65-1.69 (m, 2H), 2.08 (t, J = 7.4 Hz, 2H), 2.99 (dd, J = 13, 6.9 Hz, 2H), 3.04 (s, 9H), ), 3.24 - 3.33 (m, 2H).

The pure product is soluble in water and has surfactant properties. Halogen anions can be obtained directly from the N-alkylation reaction, and other desired counter anions can be obtained by anion exchange.

Example 2b:

Determination of Physical Properties of Surfactant 3

The critical micelle concentration (CMC) for surfactant 3 was determined. From the surface tension change with concentration in water, the CMC was determined to be about 1.6 mmol. The plateau value of the minimum surface tension achievable by this surfactant is about 20 mN/m, indicating that the surfactant has excellent surface activity. These results are plotted as surface tension versus concentration in FIG. 2 .

The dynamic surface tension of surfactant 3 was determined using a bubble pressure tensiometer, which measures the change in surface tension of the newly formed air-water interface with time. Figure 3 shows a plot of the results over time versus surface tension, demonstrating that surfactant 3 completely saturates the interface in less than 500 ms, very rapidly in terms of interfacial adsorption.

In addition to the ability of surfactant 3' to lower both interfacial and surface tension, formulations containing only surfactant have excellent wetting properties. For example, hydrophobic substrates such as polyethylene and polypropylene exhibit total surface wetting with a contact angle of 0°. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was extremely low, 10.5 ^o (Table 2).

Table 2

Example 3a:

6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6 -Synthesis of oxohexan-1-amine oxide (surfactant 4)

Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv) was added to distilled water (80 mL) in a 100 mL round bottom flask followed by 50% hydrogen peroxide (1.15 mL, 20.2 mmol, 10 equiv). The reaction was refluxed for 12 h and then concentrated in vacuo. The residue was washed 3 times with acetone to obtain surfactant 4 in 99% yield.

¹ H NMR (500 MHz, DMSO) δ 0.09 (s, 27H), 0.38-0.44 (m, 2H), 1.21-1.25 (m, 2H), 1.35-1.42 (m, 2H), 1.50-1.55 (m, 2H), 1.71-1.75 (m, 2H), 2.05-2.08 (m, 2H), 2.97-3.00 (m, 2H), 3.01 (s, 9H), 3.11 - 3.14 (m, 2H).

Example 3b:

Determination of Physical Properties of Surfactant 4

The critical micelle concentration (CMC) for surfactant 4 was determined. From the surface tension change with concentration in water, the CMC was determined to be about 0.49 mmol. The plateau value of the minimum surface tension that can be reached by this surfactant is about 20 mN/m, indicating that the surfactant has excellent surface activity. These results are plotted as surface tension versus concentration in FIG. 4 .

The dynamic surface tension of Surfactant 4 was determined using a bubble pressure tensiometer. Figure 5 shows a plot of the results over time versus surface tension and demonstrates that surfactant 4 completely saturates the newly formed air-water interface in less than 1 second, very rapidly in terms of interfacial adsorption.

In addition to the ability of Surfactant 4 to lower both interfacial and surface tension, formulations containing only Surfactant 4 at concentrations of 1-100x CMC have excellent wetting properties. For example, a solution of surfactant 4 in water at a concentration of 10x CMC exhibits a 0° contact angle for hydrophobic substrates such as polyethylene and polypropylene and a 10.6° contact angle for oleophobic and hydrophobic substrates such as Teflon. This contact angle is extremely low compared to the contact angle of water on the same substrate (Table 3).

Table 3

Example 4a:

4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxo Synthesis of hexyl)dimethylammonio)butane-1-sulfonate (surfactant 5)

Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv) was added to ethyl acetate (EtOAc) (30 mL) in a 100 mL round bottom flask followed by 1,2-butane sultone (0.27 mL, 2.2 mmol, 1.1 equiv) was added. After the reaction was refluxed for 12 hours, the solvent was removed, and the resulting white waxy solid was washed with acetone to obtain Surfactant 5 in 50% yield.

¹ H NMR (500 MHz, DMSO) δ 0.10 (s, 27H), 0.38-0.46 (m, 2H), 1.23-1.27 (m, 2H), 1.37-1.68 (m, 10H), 1.73-1.78 (m, 2H), 2.45-2.48 (m, 2H), 2.97-3.01 (m, 8H), 3.18-3.21 (m, 2H), 3.23-3.27 (m, 2H).

Example 4b:

Determination of Physical Properties of Surfactant 5

The critical micelle concentration (CMC) for surfactant 5 was determined. From the surface tension change with concentration in water, the CMC was determined to be about 0.39 mmol. The plateau value of the minimum surface tension achievable by this surfactant is about 21 mN/m, indicating that the surfactant has excellent surface activity. These results are plotted as surface tension versus concentration in FIG. 6 .

The dynamic surface tension of Surfactant 5 was determined using a bubble pressure tensiometer. 7 shows a plot of the results versus surface tension versus time and demonstrates that surfactant 5 completely saturates the newly formed air-water interface in less than 1 second, very rapidly in terms of interfacial adsorption.

Finally, a solution of surfactant 5 in water at a concentration of 10x CMC exhibits a 0° contact angle for hydrophobic substrates such as polyethylene and polypropylene and a 10.2° contact angle for oleophobic and hydrophobic substrates such as Teflon. This contact angle is extremely low compared to the contact angle of water on the same substrate (Table 4).

Table 4

Example 5:

formulation for shampoo

In this example, a formulation for use as a shampoo is provided. This formulation is useful for giving hair a smooth and soft feel. The ingredients of the formulation are presented in Table 4 below. Additionally, the formulation may include other natural oils and ingredients, as well as vitamins for consumer appeal, in amounts of less than 1% by weight.

Table 4

Example 6:

Formulations for hair conditioners

In this embodiment, a formulation for use as a hair conditioner is provided. This formulation can be used to replace or reduce polyquaternium-10, polyquaternium-7 and dimethicone oils while preserving the easy combability and soft feel provided by hair conditioners. The formulations are presented in Table 5 below.

Table 5

Example 7:

Formulations for automotive cleaning detergents to remove difficult stains from surfaces

In this embodiment, a formulation for an automobile washing detergent for removing difficult stains from a surface is provided. The formulations are presented in Table 6 below.

Table 6

Example 8:

Formulations for stain-free cleaning or drying solutions

In this example, formulations for stain-free cleaning or drying solutions are provided. The solution can be applied to the windows or body of a car after the main cleaning is complete. The formulations are presented in Table 7 below.

Table 7

Example 9:

Formulations for large carpet cleaners

In this embodiment, a formulation for a large carpet cleaner is provided. The cleaner is a high-foaming, high-level cleaner. The formulations are presented in Table 8 below.

Table 8

Example 10:

Formulations for large surface cleaners

In this example, a formulation for a large-format surface cleaner is provided. This cleaner can be used in manual or automated surface cleaning machines. The formulations are presented in Table 9 below.

Table 9

Example 11:

Formulation for dark graffiti removal detergent

In this embodiment, a formulation for a heavy graffiti removal detergent is provided. Detergent can be used on high pressure hoses. The formulations are presented in Table 10 below.

Table 10

Example 12:

Formulations for wetting agents in aerosol sprays

In this example, a formulation for a wetting agent adjuvant in an aerosol spray is provided. Aerosol sprays can be used to apply pesticides or other crop protection agents. The provided formulation aims to provide an environmentally friendly option by reducing the amount of surfactant chemicals in pesticides and crop protection agents (typically 2-5%) by providing better performance through excellent wetting and low CMC. The formulations are presented in Table 11 below.

Table 11

Example 13:

Formulation of additives for aerosol spray paints

In this embodiment, a formulation for an additive for a water-based aerosol spray paint or coating is provided. The formulation aims to provide good dynamic wetting of aerosol droplets on the surface upon application, preventing paint cratering and other such problems. The formulations are presented in Table 12 below.

Table 12

side

Aspect 1 is a compound of formula I:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

n is an integer from 1 to 12;

the terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl and C ₁ -C ₆ alkyl;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

Aspect 2 is a compound of aspect 1 represented by formula la:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

m is an integer from 1 to 6;

The terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain is selected from the group consisting of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

Aspect 3 is a compound of aspect 1 or 2 represented by formula Ib:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;

p is 5;

The terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain consists of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from the group;

An optional counterion may be associated with the compound and, if present, the counterion may be selected from the group consisting of chloride, bromide and iodide.

Aspect 4 is a compound of any one of aspects 1-3, wherein R ¹ and R ² are methyl.

Aspect 5 is a compound of aspect 1, wherein n is 5.

Aspect 6 is a compound of any one of aspects 1-5, wherein R ³ is hydrogen.

Aspect 7 is the compound of any one of aspects 1-6, wherein the counterion is selected from the group consisting of chloride, bromide and iodide.

Aspect 8 is the compound of aspect 7, wherein the counterion is chloride.

Aspect 9 is a compound of any one of aspects 1-5, wherein R ³ is methyl.

Aspect 10 is the compound of aspect 9, wherein the counterion is selected from the group consisting of chloride, bromide and iodide.

Aspect 11 is the compound of aspect 10, wherein the counterion is iodide.

Aspect 12 is a compound of any one of aspects 1-5, wherein R ³ is an oxygen atom.

Aspect 13 is a compound of any one of aspects 1-5, wherein R ³ is C ₁ -C ₆ alkyl substituted with a terminal sulfonate.

Aspect 14 is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl having the formula ) propyl) hexanamide;

.

.

Aspect 15 is 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3, wherein the compound has the formula -yl)propyl)hexaminium chloride is a compound of any one of aspects 6-8:

.

.

Aspect 15 is 3 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl) wherein the compound has the formula Amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide is a compound of any one of aspects 9-11:

.

.

Aspect 17 is 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)- is a compound of aspect 12 which is N,N-dimethyl-6-oxohexan-1-amine oxide:

.

.

Aspect 18 is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl having the formula is a compound of aspect 13, which is )amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate:

.

.

Aspect 19 is 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl having the formula is a compound of aspect 13, which is )amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate:

.

.

Claims (19)

Compounds of formula (I):

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;
n is an integer from 1 to 12;
the terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl and C ₁ -C ₆ alkyl;
An optional counterion may be associated with the compound, the counterion, if present, selected from the group consisting of chloride, bromide and iodide. 2. The compound according to claim 1, which is represented by formula Ia:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;
m is an integer from 1 to 6;
the terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain is selected from the group consisting of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from;
An optional counterion may be associated with the compound, the counterion, if present, selected from the group consisting of chloride, bromide and iodide. 2. The compound according to claim 1, represented by formula Ib:

wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl being one or more of oxygen, nitrogen or sulfur atoms. , or a group comprising at least one of these atoms, wherein the alkyl chain is one selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl and carboxylate. may be optionally substituted with one or more substituents;
p is 5;
The terminal nitrogen is optionally further substituted with R ³ , wherein R ³ is selected from the group consisting of hydrogen, oxygen, and C ₁ -C ₆ alkyl, wherein the alkyl chain consists of carboxyl, carboxylate and sulfonate. optionally substituted with one or more substituents selected from the group;
An optional counterion may be associated with the compound, the counterion, if present, selected from the group consisting of chloride, bromide and iodide. The compound of claim 1 , wherein R ¹ and R ² are methyl. 2. The compound of claim 1, wherein n is 5. 6. The compound of claim 5, wherein R ³ is hydrogen. 7. The compound of claim 6, wherein the counterion is selected from the group consisting of chloride, bromide and iodide. 8. The compound of claim 7, wherein the counterion is chloride. 6. The compound of claim 5, wherein R ³ is methyl. 10. The compound of claim 9, wherein the counterion is selected from the group consisting of chloride, bromide and iodide. 11. The compound of claim 10, wherein the counterion is iodide. 6. A compound according to claim 5, wherein R ³ is an oxygen atom. 6. The compound of claim 5, wherein R ³ is C ₁ -C ₆ alkyl substituted with sulfonate. 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane- Compounds that are 3-yl)propyl)hexanamide:

. 9. The 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane- Compounds that are 3-yl)propyl)hexaminium chloride:

. 12. The 3 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl of claim 11 having the formula Compounds which are )amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide:

. 13. 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl) according to claim 12 having the formula Compounds that are amino)-N,N-dimethyl-6-oxohexan-1-amine oxide:

. 14. The 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3- A compound that is yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate:

. 14. The 5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3- A compound that is yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate:

.

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